JPS6031353B2 - Primer composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to primer compositions.

Specifically, the present invention relates to a primer composition that has excellent adhesive properties and water resistance, and is widely applicable to both substrates and adhesives/sealants. When using adhesives and sealants that require strong adhesive strength, such as thiol-based, silicone-based, or urethane-based adhesives, chlorinated paraffin is added to chlorinated rubber to ensure strong adhesion to various substrates. Primers are used in combination with plasticizers such as

In particular, this chlorinated rubber type is compatible with porous and alkaline environmental substrates such as concrete mortar, calcium citrate board, and slate board, and is widely used as a primer. Since adhesion is not sufficient, the current situation is to use polyisocyanates in combination to improve adhesive strength.

However, the combined use of these chlorinated rubbers and polyisocyanates can improve the adhesion of urethane-based and thiol-based adhesives and sealants during normal use, but the adhesive surface can easily peel off due to water intrusion. It has the disadvantage of causing

In addition, some silicone-based adhesives and sealants use a silane coupling agent in order to ensure compatibility with the primer and silicone resin, but since the adhesion varies depending on the curing type of the silicone resin, It is necessary to use a different type of primer depending on whether it is an acid type, a dehydroxyamine type, or a deoxime type, and furthermore, when immersed in water in an alkaline liquid, the adhesive strength tends to be extremely reduced. Therefore, there is a need for a primer that is versatile and has excellent water resistance and alkali resistance for both base materials, adhesives, and sealants. An object of the present invention is to provide such a versatile primer composition and excellent water resistance and alkali resistance. The primer composition of the present invention contains, as essential components, a chlorinated polymer (1), an organic polyisocyanate (b), and a modified pentadiene polymer (m), or these (1),
It is characterized by containing (D), (m) and a silane coupling agent (W).

The chlorinated polymer (1) which is an essential component of the present invention includes various chlorinated rubbers, ie, chlorinated products of natural rubber,
Chlorinated products of isoprene-based synthetic rubber, chlorinated products of homopolymers or polymers of olefins such as ethylene and propylene, chlorinated products of homopolymers or copolymers of butadiene, styrene, etc., chlorinated paraffins, and post-chlorinated products of chloroprene. etc. Chlorinated polymerized K of the present invention
I) can be used if it has a chlorine content of 10 to 80%, but it is preferable because if the chlorine content is too low, water resistance will decrease, and the cohesive force of the primer and various stability. The one having a chlorination degree of 50 to 75% is used.

The organic polyisocyanate (0) which is another essential component of the present invention includes commonly used isocyanates such as methylene diisocyanate, toluene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. All can be used, and derivatives of the isocyanate with polyhydric alcohols such as trimethylolpropane, amines such as methylene diamine, lysine isocyanate, methyl ester, etc. can also be used. Among these polyisocyanates, commercially available products such as Dismode Yulu N and Dismode Yuru HL (manufactured by Bavarian AG) are considered to be easy to handle in terms of stability and viscosity.

If the amount of the organic polyisocyanate (m) used is too small, it will not have adhesive strength to urethane-based or thiokol-based adhesives or sealants, and if it is too large, it will react rapidly with moisture in the air, etc. 5 to 10 chlorinated polymers (1) (by weight, the same shall apply hereinafter) to facilitate gelation.
It is best to use about 0 to 30 foundations. The modified pentadiene polymer (m), which is another essential component of the present invention, has an iodine value of 200 to 500 and an average molecular weight of 350 to 10,000.
This is a modified pentadiene polymer obtained by introducing an epoxy group and a hydroxy group (some of which may be substituted with an acyloxy group) into a 1,3-bentadiene homopolymer or a copolymer thereof.

The modified pentadiene polymer (m) is obtained by polymerizing 1,3-bentadiene or other copolymer components (for example, isoprene, isoptylene, styrene, etc.).
Preferably an iodine value obtained by cationic polymerization of 200 to
500, average molecular weight 350-10000, preferably 5
00-3000 liquid polymer (preferably 30-40% 1,4 bonds, 60-70% 1,2 and 3,4 bonds)
%, with a cis/trans bond ratio of 12/88 to 20
/80.

) can be obtained, for example, by the method shown in Tokuya Sho 49-197093, that is, by reacting it with aqueous hydrogen peroxide in the presence of a lower carboxylic acid. The introduction ratio of epoxy equivalent is 240 to 1200, preferably 300.
-80Q hydroxyl equivalent is 300-5000 preferably 50
It is preferably between 0 and 3000. The above-mentioned modified pentadiene polymer dish) consists of 10 anchor parts of chlorinated polymer (1), 5
~30 anchorages are used, preferably 10-15 anchorages.

Next, the silane coupling agent (W) that can be used in the present invention
Examples include those having an epoxy group, an amino group, or a thiol group, such as y-glycidoxypropyltrimethoxysilane, y-glycidoxypropylmethyldimethoxysilane, 3,4 epoxycyclohexylethyltrimethoxysilane, , 4-epoxycyclohexylethylmethyldimethoxysilane, aminomethyltriethoxysilane, N-(8-aminoethyl)aminomethyltrimethoxysilane, N-(3-aminoethyl)methyltributoxysilane, y-aminopropyltriethoxysilane ,y-
Aminopropylmethyldiethoxysilane, y-aminoisobutyltrimethoxysilane, y-mercaptopropyltrimethoxysilane, N-bis(3-hydroxyethyl)-so-aminopropyltriethoxysilane, N-(8
-aminoethyl)-y-aminopropyltrimethoxysilane, N-(8-aminoethyl)-y-aminopropylmethyldimethoxysilane, N-(8-aminoethyl)-
Examples include tuamino-8-methylpropyltrimethoxysilane.

These silane coupling agents may be added alone, but in order to achieve further effects such as water resistance, they may be added in advance with modified pentadiene polymerization m) or organic polyisocyanate m) without a catalyst or If necessary, it may be used after carrying out a reaction using a catalyst such as a tertiary amine, metal oxide, phenol, or resorcinol.

These silane coupling agents (W) are chlorinated polymers (
1) It is possible to use 2 to 30 anchors for 10 anchors, but if too many, the film strength may be reduced, so preferably 2 to 10 anchors are used. The silane coupling agent (W) can increase the affinity with the primer, especially when used for adhesives and sealants with low affinity, and when used for adhesives such as glass plates, the Moreover, it can maintain excellent physical properties even under harsh conditions.

The primer composition of the present invention can also contain other additives, such as weather resistance and workability improvers. , glass powder, molecular sheep, calcium carbonate, etc. may be blended.

To formulate the primer composition of the present invention, non-polar hydrocarbon-based, ketone-based, ester-based, ether-based, etc. solvents that do not have active hydrogen can be used. can be adjusted appropriately.

Such solvents include benzene, toluene, xylene, methylene chloride, /gucrene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, ethyl ether, tetrahydrofuran, dioxane, butyl cellosolve, Carbitol, ethylene glycol mo/ethyl ether acetate, etc. can be used alone or in combination. The primer composition of the present invention has good adhesive properties, water resistance, and water resistance, and can be used with various adhesives and sealants such as silicone-based, thiol-based, and urethane-based, and with various materials such as concrete, mortar, aluminum, and glass plates. It has excellent workability and versatility and can be widely applied.

Hereinafter, the present invention will be further explained by examples.

In addition, "parts" in the examples represent "parts by weight."

Production Example 1 Modified Pentadiene Polymer■ A cationically polymerized liquid polybentagene with an average molecular weight of 500 and an iodine value of 360 was dissolved in 742.5 parts of chloroform, and 92.8 parts of 80% formic acid and 1 part of phosphoric acid were dissolved in this. In addition, the temperature was raised to 6,000 ℃ under the rope frame, and 17.4 parts of hydrogen peroxide was added to about 1. It was dropped at the morning temple and kept at the same temperature for 5 hours after dropping.

After the reaction, the resin was washed with water and the solvent was removed until the pH reached 7 to obtain a resin.

Yield: 518 parts, epoxy equivalent: 453.4, hydroxyl equivalent: 1
It was a viscous liquid of 512.1.

Production Example 2 Modified Pentadiene Polymer ■ A cationically polymerized liquid copolymer containing % by weight of 1,3-pentadiene 8 with a molecular weight of 1000 and % by weight of butadiene 2 (
Iodine value: 400) 30 parts of Ikarito was dissolved in 900 parts of chloroform, heated to 60 qo of 80% formic acid, and 177 parts of 80% formic acid was dissolved.
6 parts of phosphoric acid, 0.6 parts of phosphoric acid, and 197.4 parts of 60% hydrogen peroxide solution were added dropwise over 4 hours at the same temperature.

After dropping, the resin was treated in the same manner as in Production Example 1 to obtain a resin. Yield 360
parts, epoxy equivalent weight 405.5, hydroxyl equivalent weight 800, softening point 75-85 ○Production example 3 Modified pentadiiso polymer 1
Melt 50 pieces of Takubu and raise the temperature to 60 q0, 80%
A solution of 85 parts of formic acid, 2 parts of phosphoric acid, and 171 parts of 6000 hydrogen peroxide solution were added dropwise over 4 hours at the same temperature.

After dropping, the resin was treated in the same manner as in Production Example 1 to obtain a resin. Yield 509
parts, epoxy equivalent weight 371, hydroxyl equivalent weight 1764, softening point 30-45 qo Production example 4 Modified pentadiene polymer■ A cationically polymerized liquid polybentadiene polymer having a molecular weight of 2000, 50 parts dissolved in 1600 parts of chloroform,
The temperature was raised to 60qC under Danyo, and 282.6 parts of 80% formic acid was added.
A concentrated solution of 1 part of phosphoric acid and 304 parts of 60% hydrogen peroxide solution were added dropwise at the same temperature over 4 hours.

After dropping, the resin was treated in the same manner as in Production Example 1 to obtain a resin. Yield 610
parts, epoxy equivalent: 400, hydroxyl equivalent: 930, softening point: 7
0 to 8000 Production Example 5 Modified Pentadiene Polymer■ Cationically polymerized liquid polybentadiene polymer with a molecular weight of 2000, (iodine value 360) 50 parts of chloroform
The temperature was raised to 60oC under Takaazusa, and a mixed solution of 35 parts of 80% formic acid, 1 part of phosphoric acid, and 311 parts of 60% hydrogen oxide solution were added dropwise at the same temperature over 3 hours.

After dropping, the resin was treated in the same manner as in Production Example 1 to obtain a resin. Yield 650
parts, epoxy equivalent weight 73, hydroxyl equivalent weight 560, softening point 90-100 qo Comparative production example 1 Polybutadiene with molecular weight 1000 (iodine value 380) 3
0 country was dissolved by 30 chloroforms and 1 anchor, and 6 bases were added.
The temperature was raised to 0qo, and 32 parts of 80% formic acid and 0.3 parts of phosphoric acid were added.
A mixed solution of 50% and 16% 60% hydrogen oxide solution was added dropwise over about 5 hours, and the temperature was kept at the same temperature for 3 hours after the addition.

After the reaction, the mixture was washed with water until the pH reached 7, and the solvent was removed to obtain a liquid resin. Yield: 35, epoxy equivalent: 167, hydroxyl equivalent: 5,610 Comparative Examples 1 to 7 Examples 1 to 19 Primers having the composition shown in Table 1 were used in accordance with JIS-R-5201.
Apply two coats with a brush to the surface of mortar plates and untreated aluminum plates made according to the JIS standard.
A test piece for tensile adhesion was prepared in accordance with A-5755, filled with a sealant, and left for sufficient time to cure each sealant (7 days at room temperature).
After soaking for 0 days, after soaking in 3% caustic soda solution for 10 days, and after irradiating for 1000 hours with a Sunshine Weatherometer tester (WE-SUN 1 day CA-1 model manufactured by Suga Test Instruments Co., Ltd.), the adhesive strength was determined. Measured (Tensile speed, 50 side/mi
n).

The results are shown in Table 2-■ to ◎. As shown in Table 2, all primers exhibit strong adhesive strength under normal conditions even when used with various sealants.

However, the sample of the comparative primer after the hot water immersion test, alkali resistance test, and superiority resistance test easily caused interfacial peeling between the primer and the sealant.
The primer of the present invention to which the modified pentadiene polymer was added did not cause a decrease in adhesive strength, did not cause interfacial peeling as in the normal state, and caused rubber failure of the sealant itself. As for the storage stability of the primer, as shown in Table 1, it had a viscosity that allowed brushing even when stored at 50°C for 30 days, and no abnormalities were observed for more than 3 months at room temperature. Regarding the alkali resistance of the primer itself, we applied it to an asbestos slate board, air-dried it for one day, put a cross cut in it, soaked it in 5% caustic soda for 30 days, and then performed a tape peel test, but it was modified to a system using chlorinated rubber. The system of the present invention with the addition of pentadiene polymer did not cause whitening of the arms.

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The tensile strength was tested in the same manner as in Example 1.

That is, Examples 1 to 1 for mortar and aluminum plate
After curing for a predetermined period of time, the primer and sealant were partially peeled off with a knife and further peeled off manually, and the results were evaluated as follows. ○ The sealant was cut without peeling between the primer and the sealant.

× It was easy to get angry between the primer and sealant.

The water condensation resistance test was conducted by immersing the sample in 9800 hot water for 8 hours, and then conducting the same adhesion test.

The results are shown in Table 4. As shown in Table 4, the primer of the present invention is a one-component primer that exhibits sufficient adhesive strength to mortar and aluminum plates, and has excellent effects on boiling water resistance, alkali resistance, and stiffness resistance. was expressed. Also, among the primers shown in Table-3, P-2
0, 126, 127, 128, 133, 137 and Co
8 to 12 were applied to asbestos slate boards, calcium citrate boards, stainless steel (SuS-304), bonded steel plates, European steel plates with acrylic paint baked on, epoxy molded products, and glass plates, and after air drying for 1 hour, each sealant was applied. Apply the agent to a thickness of about 5 skins and immerse it in normal and boiling water (980
The adhesion after 2002 German time was tested.

The results are shown in Table-5. As shown in Table 5, the primer of the present invention caused rubber failure in all base materials. In addition, a primer using the resin of Comparative Production Example-1 (
Co-8,9) showed strong adhesion to asbestos slate boards in the polysulfide sealant (commercially available sealant B), but after the vertical water test, interfacial peeling between the primer and the sealant occurred.

Comparative example primer Co using a silane coupling agent
-12, a two-component silicone sealant (commercially available sealant C) and a one-component silicone sealant (commercially available sealant A) include asbestos slate board, calcium citrate board, stainless steel, bonded steel plate, It showed adhesion to acrylic paint-baked boards, epoxy molded products, and glass plates, but interfacial peeling was observed after the weaving water test, and it was normal to polysulfide sealants (commercially available sealant B) and urethane sealants. However, no effect was shown.

Furthermore, if the primer specified by each sealant manufacturer is used on a predetermined base material and other than the sealant, it will not exhibit adhesive properties even under normal conditions.

Thus, the primer of the present invention has wide versatility. Armor S Humiliation/T'i↑, - Satoshi Ant ■ Ship Rei Ri Raku ■ Shortcut 9 Kitomun entry★ 'To ○ l Kokan ≦ ÷ Shikōho N N ■ X Mon■ Ship

Claims (1)

[Claims] 1 As essential constituents, chlorinated polymer (I), organic polyisocyanate (II), and modified pentadiene polymer (III), or these (I), (II), (III)
and a silane coupling agent (IV).